NCERT Textbook Questions

NCERT Intext Questions

Q. 1. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can you say that it is a
transition element?
Ans. Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (4d), hence
a transition element.
Q. 2. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e.,
126 kJ mol–1. Why?
Ans. In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc, while in all
other metals of the 3d series, electrons from the d-orbitals are always involved in the formation of metallic
bonds. That is why, the enthalpy of atomisation of zinc is the lowest in the series.
Q. 3. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?
Ans. Manganese (Z = 25), as it has the maximum number of unpaired electrons in d-subshell. Thus, it shows
oxidation states from +2 to +7 (+2, +3, +4, +5, +6 and +7) which is the maximum number.
Q. 4. The Eo (M2+/M) value for copper is positive (+0.34 V). What is possible reason for this?
(Hint: Consider its high D a H 6 and low Dhyd H 6)
Ans. Eo (M2+/M) for any metal is related to the sum of the enthalpy change taking place in the following steps:
M(s) + Da H M(g), (Da H = Enthalpy of atomisation)
2+
M(g) + Di H M (g), (Di H = Ionisation enthalpy)
M2+(g) + aq M2+(aq) + DhydH, (Dhyd H = Hydration enthalpy)
Copper has high enthalpy of ionisation and relatively low enthalpy of hydration. So, E(oCu2+ /Cu) is positive.
The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.
Q. 5. How would you account for the irregular variation of ionisation enthalpies (first and second) in first
series of the transition elements?
Ans. Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d
configuration (e.g., d 0 , d 5 , d 10 are exceptionally stable).
Q. 6. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Due to small size and high electronegativity, oxygen or fluorine can oxidise a metal to its highest oxidation
state. As a result of this they can oxidise a metal to its highest oxidation state.
Q. 7. Which is a stronger reducing agent— Cr2+ or Fe2+ and why? [HOTS]
Ans. Cr is a stronger reducing agent than Fe because after the loss of one electron Cr becomes Cr3+ which
2+ 2+ 2+

has more stable t 32g (half-filled) configuration in a medium like water.

Q. 8. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
OR
Calculate the spin-only magnetic moment of Co2+(Z=27) by writing the electronic configuration of Co
and Co2+. [CBSE 2020 (56/1/1)]
Ans. Electronic configuration of M atom with Z = 27 is [Ar] 3d 7 4s 2 .
\ Electronic configuration of M2+ = [Ar] 3d 7, i.e.,
Hence, it has three unpaired electrons.
\ Spin only magnetic moment (µ) = n(n + 2) BM
= 3(3 + 2) BM = 15BM = 3.87 BM
+
Q. 9. Explain why Cu ion is not stable in aqueous solutions? [HOTS]
Ans. In aqueous solution Cu+ undergoes disproportionation to form a more stable Cu2+ ion.
2Cu+ (aq) Cu2+(aq) + Cu(s)
The higher stability of Cu in aqueous solution may be attributed to its greater negative Dhyd.Ho than that
2+

of Cu+. It compensates the second ionisation enthalpy of Cu involved in the formation of Cu2+ ions.

310 Xam idea Chemistry–XII

Q. 10. Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Ans. This is because the 5f electrons themselves provide poor shielding from element to element in the series.

NCERT Textbook Exercises

Q. 1. Write down the electronic configuration of
(i) Cr3+ (ii) Cu+ (iii) Co2+ (iv) Mn2+ (v) Pm3+
(vi) Ce4+ (vii) Lu2+ (viii) Th4+
3+ 3
Ans. (i) Cr = [Ar] 3d (ii) Cu+ = [Ar] 3d 10
(iii) Co2+ = [Ar] 3d 7 (iv) Mn2+ = [Ar] 3d 5
(v) Pm3+ = [Xe] 4f 4 (vi) Ce4+ = [Xe]
(vii) Lu2+ = [Xe] 4f 14 5d 1 (viii) Th4+ = [Rn]
Q. 2. Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their +3 state?
Ans. Electronic configuration of Mn2+ is 3d 5 which is half-filled and hence stable. So, 3rd ionisation enthalpy is
very high, i.e., 3rd electron cannot be easily lost. In case of Fe2+, electronic configuration is 3d 6. Thus, it
can lose one electron easily to give the stable configuration 3d 5.
Q. 3. Explain briefly how +2 state becomes more and more stable in the first half of the first row transition
elements with increasing atomic number.
Ans. As the atomic number increases from 21 to 25, the number of electrons in the 3d-orbital also increases from
1 to 5. +2 oxidation state is attained by the loss of the two 4s electrons by these metals. Sc does not exhibit
+2 oxidation state. As the number of d- electrons in +2 state increases from Ti to Mn, the stability of +2
state increases (d-orbital gradually becoming half filled). Mn(+2) has d 5 electrons which is highly stable.
Q. 4. To what extent do the electronic configurations decide the stability of oxidation states in the first
series of the transition elements? Illustrate your answer with example.
Ans. The stability of oxidation states in the first series of the transition elements are related to their electronic
configurations.
The first five elements of the first transition series up to Mn in which the 3d-subshell is not more than
half-filled, the minimum oxidation state is given by the number of electrons in the outer s-subshell and the
maximum oxidation state is given by the sum of the outer s and d-electrons. For example, Sc does not
show +2 oxidation state. Its electronic configuration is 3d 1 4s2. It loses all the three electrons to form
Sc3+. +3 oxidation state is very stable as by losing all three electrons, it attains the stable configuration of
Argon. For Mn, +2 oxidation state is very stable, as after losing two 4s electrons, the d-orbitals become
half-filled.
Q. 5. What may be the stable oxidation state of the transition element with the following d-electron
configuration in the ground state of their atoms?
3d 3 , 3d 5 , 3d 8 and 3d 4
Ans. Stable oxidation states:
3d 3 (vanadium): +2, +3, +4, +5 3d 5 (chromium): +3, +4, +6
3d 5 (manganese): +2, +4, +6, +7 3d 8 (nickel): +2, +4
4 4
3d : There is no d configuration in the ground state.
Q. 6. Name the oxo-metal anions of the first series of the transition metals in which the metal exhibits the
oxidation state equal to its group number.
Ans. Cr2O72– and CrO42– (group no. = oxidation state of Cr = 6)
MnO4– (group no. = oxidation state of Mn = 7)
Vanadate: VO3– (group no. = oxidation state of V = 5)
Q. 7. What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
Ans. Refer to Basic Concepts Point 5 (v).
The consequences of lanthanoid contraction are as follows:
(i) The properties of second and third transition series are similar.

The d- and f- Block Elements 311

 (ii) Basic strength decreases from La(OH)3 to Lu(OH)3.
(iii) Lanthanide contraction makes separation of lanthanoids possible.
Q. 8. What are the characteristics of the transition elements and why are they called transition elements?
Which of the d-block elements may not be regarded as the transition elements?
Ans. Characteristics of the transition elements: Refer to Basic Concepts Point 3.
The d-block elements are called transition elements because these elements represent change (or
transition) in properties from the most electropositive s-block elements to the least electropositive
p-block elements.
The electronic configuration of Zn, Cd and Hg are represented by the general formula (n – 1) d 10 ns 2. The
orbitals in these elements are completely filled in the ground state as well as in their common oxidation
states. Therefore, they are not regarded as transition elements.
Q. 9. In what way is the electronic configuration of transition elements different from that of the non-
transition elements?
Ans. Transition elements contain incompletely filled d-subshell, i.e., their electronic configuration is
(n – 1) d 1 – 10 ns1 – 2 whereas non-transition elements have no d-subshell or their subshell is completely
filled and have ns1 – 2 or ns2 np1 – 6 in their outermost shell.
Q. 10. What are the different oxidation states exhibited by lanthanoids?
Ans. +2, +3 and +4 (+3 being most common).
Q. 11. Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
Ans. (i) Refer to Basic Concepts Point 3(h).
(ii) The transition elements exhibit high enthalpy of atomisation because they have large number of
unpaired electrons in their atoms. Due to this they have stronger interatomic interaction.
(iii) Refer to Basic Concepts Point 3(k).
(iv) The transition metals and their compounds are known for their catalytic activity. This activity is
due to their ability to adopt multiple oxidation states and to form complexes. Vanadium oxide (in
Contact Process), finely divided iron (in Haber’s Process), and nickel (in catalytic hydrogenation)
are some examples to mention. Catalysts at a solid surface involve the formation of bonds between
reactant molecules and atoms of the surface of the catalyst (first row transition metals utilise 3d and
4s electrons for bonding). This has the effect of increasing the concentration of the reactants at the
catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is
lowering). Also, since the transition metal ions can change their oxidation states, they become more
effective as catalysts. For example, iron(III) catalyses the reaction between iodide and persulphate ions.
2I – + S2O82– I2 + 2SO42–
An explanation of this catalytic action is given as under:
2Fe3+ + 2I – 2Fe2+ + I2
2Fe2+ + S2O82– 2Fe3+ + 2SO42–
Q. 12. What are interstitial compounds? Why are such compounds well known for transition metals?
Ans. Interstitial compounds are those in which small atoms occupy the interstitial sites in the crystal lattice.
Interstitial compounds are well known for transition metals because small-sized atoms of H, B, C, N, etc.,
can easily occupy positions in the voids present in the crystal lattices of transition metals.
Q. 13. How is the variability in oxidation states of transition metals different from that of the non transition
metals? Illustrate with examples.
Ans. The oxidation states of transition elements differ from each other by unity e.g., Fe2+ and Fe3+, Cu+ and Cu2+
(due to incomplete filling of d-orbitals) whereas oxidation states of non-transition elements normally differ
by two units e.g., Pb2+ and Pb4+, Sn2+ and Sn4+, etc.

312 Xam idea Chemistry–XII

Q. 14. Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate?
Ans. For preparation of potassium dichromate from iron chromite ore refer to Basic Concepts Point 4(a).
In aqueous solution, dichromate and chromate ions exist in equilibrium. On increasing the pH, i.e., on
making the solution alkaline, dichromate ions (orange coloured) are converted into chromate ions and thus,
the solution turns yellow.
Q. 15. Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction
with (i) iodide (ii) iron (II) solution (iii) H2S.
Ans. (i) Cr2O72– + 14H+ + 6I – 2Cr3+ + 7H2O + 3I2
(ii) Cr2O72– + 14H+ + 6Fe2+ 2Cr3+ + 7H2O + 6Fe3+
(iii) Cr2O72– + 8H+ + 3H2S 2Cr3+ + 7H2O + 3S
Q. 16. Describe the preparation of potassium permanganate. How does the acidified permanganate react
with (i) iron (II) ions (ii) SO2 (iii) oxalic acid? Write the ionic equations for the reaction.
Ans. For preparation, refer to Basic Concepts Point 4(b).
(i) MnO4– + 8H+ + 5Fe2+ Mn2+ + 4H2O + 5Fe3+
(ii) 2MnO4– + 2H2O + 5SO2 2Mn2+ + 4H+ + 5SO42–
–
COO
(iii) 2MnO4– + 16H+ + 5 | 2Mn2+ + 8H2O + 10CO2
–
COO
Q. 17. For M2+/M and M3+/M2+ systems, Eo values for some metals are as follows:
Cr2+/Cr = – 0.9 V Cr3+/Cr2+ = – 0.4 V
Mn2+/Mn = – 1.2 V Mn3+/Mn2+ = +1.5 V
2+
Fe /Fe = – 0.4 V Fe3+/Fe2+= +0.8 V [CBSE Sample Paper 2016]
Use this data to comment upon
(i) the stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+.
(ii) the ease with which iron can be oxidised as compared to the similar process for either Cr or Mn
metals.
Ans. (i) Higher the reduction potential of a species, greater is the ease with which it undergo reduction. Among
these pairs, Mn3+/Mn2+ has largest positive reduction potential. Hence Mn3+ can be easily reduced to
Mn2+ i.e., Mn3+ is least stable. Cr3+/Cr2+ has a negative Eo value, therefore, Cr3+ is most stable. Fe3+/Fe2+
has a positive value but small. Hence, Fe3+ is more stable than Mn3+ but less stable than Cr3+.
(ii) Lower the reduction potential or higher the oxidation potential of a species, greater is the ease with
which it undergo oxidation. Among these pairs, Mn2+/Mn has the most negative reduction potential
or most positive oxidation potential. Therefore, it will be most easily oxidised. Thus, the decreasing
order of their ease of oxidation is Mn > Cr > Fe.
Q. 18. Predict which of the following will be coloured in aqueous solution?
Ti 3+, V 3+, Cu +, Sc 3+, Mn 2+, Fe 3+, Cq 2+ . Give reasons for each.
Ans. An ion is coloured when it has one or more unpaired electrons. Thus, Ti3+, V3+, Mn2+, Fe3+ and Co2+ are
coloured, due to the presence of unpaired electrons and d-d transitions. Cu+ and Sc3+ are colourless.
Q. 19. Compare the stability of +2 oxidation state for the elements of the first transition series.
Ans. Refer to Ans. 3. of NCERT Textbook Exercises.
Q. 20. Compare the chemistry of actinoids with that of lanthanoids with special reference to
(i) electronic configuration (ii) oxidation states
(iii) atomic and ionic sizes (iv) chemical reactivity.
OR
Give three points of difference between lanthanoids and actinoids. [CBSE 2020 (56/1/1)]
Ans. (i) Electronic configuration: The general electronic configuration of lanthanoids is [Xe]54 4f 1–14 5d 0 –1 6s2
whereas that of actinoids is [Rn]86 5f 1 – 14 6d 0 – 1 7s2. Thus, lanthanoids belong to 4f-series whereas
actinoids belong to 5f-series.

The d- and f- Block Elements 313

 (ii) Oxidation states: Lanthanoids show limited oxidation states (+2, +3, +4), out of which, +3 is most
common. This is because of a large energy gap between 4f, 5d and 6s subshells. On the other hand,
actinoids show a large number of oxidation states because of small energy gap between 5f, 6d and 7s
subshells.
(iii) Atomic and ionic sizes: Both show decrease in size of their atoms or ions in +3 oxidation state. In
lanthanoids, the decrease is called lanthanoid contraction whereas in actinoids, it is called actinoid
contraction. However, the contraction is greater from element to element in actinoids due to poorer
shielding by 5f-electrons.
(iv) Chemical reactivity:
Lanthanoids: In general, the earlier members of the series are quite reactive (similar to calcium) but
with increasing atomic number, they behave more like aluminium.
Values for Eo for the half-reaction:
Ln3 +(aq) + 3e– Ln(s) Ln2O3
H2

bu
are in the range of –2.2 to –2.4 V except

rn

s
s

id
for Eu for which the value is –2.0 V. This

in

ac
O2

ith
is ofcourse, a small variation.

w
The metals combine with hydrogen when heated with S with halogens
gently heated in the gas. The carbides, Ln2S3 Ln LnX3
Ln3C, Ln2C3 and LnC2 are formed when

2
N
the metals are heated with carbon. They

ith

wi
w

th
liberate hydrogen from dilute acids and

2773 K
ed

with C

H2
at

O
he
burn in halogens to form halides. They
form oxides and hydroxides—M2O3 and
M(OH)3. The hydroxides are definite LnN Ln(OH)3 + H2
compounds, not just hydrated oxides, Ln3C, LnC2, Ln2C3
basic like alkaline earth metal oxides and Chemical reactions of the lanthanoids
hydroxides.
Actinoids: The actinoids are highly reactive metals, especially when finely divided. The action of
boiling water on them, for example, gives a mixture of oxide and hydride and combination with most
non-metals takes place at moderate temperatures. Hydrochloric acid attacks all metals but most are
slightly affected by nitric acid owing to the formation of protective oxide layers; alkalis have no action.
Actinoids are more reactive than lanthanoids due to bigger atomic size and lower ionisation energy.
Q. 21. How would you account for the following:
(i) Of the d 4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily
oxidised.
(iii) The d1 configuration is very unstable in ions.
Ans. (i) E° value for Cr3+/Cr2+ is negative (–0.41 V) whereas E° value for Mn3+/Mn2+ is positive (+1.57 V).
Thus, Cr2+ ions can easily undergo oxidation to give Cr3+ ions and, therefore, act as strong reducing
agent. On the other hand, Mn3+ can easily undergo reduction to give Mn2+ and hence act as oxidising
agent.
(ii) This is because in presence of complexing reagents the CFSE value compensates more than the third
ionisation energy of cobalt.
(iii) The ions with d 1 configuration have the tendency to lose the only electron present in d-subshell to acquire
stable d 0 configuration. Therefore, they are unstable and undergo oxidation or disproportionation.
Q. 22. What is meant by ‘disproportionation’? Give two examples of disproportionation reaction in aqueous
solution.
Ans. Disproportionation reactions are those reactions in which the same substance undergoes oxidation as well
as reduction. In disproportionation reaction, oxidation number of an element increases as well as decreases
to form two different products. For example,

314 Xam idea Chemistry–XII

 VI VII IV
3MnO42– + 4H +
2MnO4– + MnO2 + 2H2O
V VI III
3CrO43– + 8H +
2CrO42– + Cr3+ + 4H2O
Q. 23. Which metal in the first transition series exhibits +1 oxidation state most frequently and why?
Ans. Cu has the electronic configuration 3d10 4s1. It can easily lose 4s1 electron to give the stable 3d10
configuration. Hence, it shows +1 oxidation state.
Q. 24. Calculate the number of unpaired electrons in the following gaseous ions:
(i) Mn3+, (ii) Cr3+, (iii) V3+ and (iv) Ti3+.
Which one of these is the most stable in aqueous solution?
Ans. (i) Mn3+ = 3d 4 = 4 unpaired electrons (ii) Cr3+ = 3d 3 = 3 electrons
3+ 2
(iii) V = 3d = 2 electrons (iv) Ti3+ = 3d 1 = 1 electron.
Cr3+ is the most stable in aqueous solution because it has half-filled t2g level (i.e., t32g).
Q. 25. Give example and suggest reasons for the following features of the transition metal chemistry:
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxo-anions of a metal.
Ans. (i) The lowest oxide of transition metal is basic because the metal atom has low oxidation state. This
means that it can donate valence electrons which are not involved in bonding to act like a base.
Whereas the highest oxide is acidic due to the highest oxidation state as the valence electrons are
involved in bonding and are unavailable. For example, MnO is basic whereas Mn2O7 is acidic.
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides because oxygen and fluorine
are highly electronegative elements, small in size (and strongest oxidising agents). For example, osmium
shows an oxidation states of +6 in OsF6 and vanadium shows an oxidation state of +5 in V2O5.
(iii) Oxometal anions have the highest oxidation state, e.g., Cr in Cr2 O72– has an oxidation state of +6
whereas Mn in MnO 4– has an oxidation state of +7. This is again due to the combination of the metal
with oxygen, which is highly electronegative and oxidising element.
Q. 26. Indicate the steps in the preparation of
(i) K2Cr2O7 from chromite ore.
(ii) KMnO4 from pyrolusite ore.
Ans. (i) Refer to Basic Concepts Point 4(a).
(ii) Refer to Basic Concepts Point 4(b).
Q. 27. What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
Ans. An alloy is a homogeneous mixture of two or more metals, or metals and non-metals. An important alloy
containing lanthanoid metals is misch metal which contains 95% lanthanoid metals and 5% iron alongwith
traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter flints.
Q. 28. What are inner-transition elements? Decide which of the following atomic numbers are the numbers
of the inner-transition elements: 29, 59, 74, 95, 102, 104.
Ans. The f-block elements, i.e., in which the last electron enters into f-subshell are called inner-transition
elements. These include lanthanoids (58–71) and actinoids (90–103). Thus, elements with atomic numbers
59, 95 and 102 are inner-transition elements.
Q. 29. The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this
statement by giving some examples from the oxidation state of these elements.
Ans. Lanthanoids show a limited number of oxidation state, viz., +2, +3 and +4 (out of which +3 is the most
common). This is because of a large energy gap between 4f, 5d and 6s subshells. The dominant oxidation
state of actinoids is also +3 but they show a number of other oxidation states also, e.g., uranium (Z = 92)
and plutonium (Z = 94) show +3, +4, +5 and +6, neptunium (Z = 94) shows +3, +4, +5 and +7, etc. This is
due to small energy difference between 5f, 6d and 7s subshells of the actinoids.

The d- and f- Block Elements 315

Q. 30. Which is the last element of the series of the actinoids? Write the electronic configuration of this
element. Comment on the possible oxidation state of this element.
Ans. Last actinoid = Lawrencium (Z = 103)
Electronic configuration = [Rn]86 5f 14 6d 1 7s2
Possible oxidation state = +3
Q. 31. Use Hund’s rule to derive the electronic configuration of Ce3+ ion and calculate its magnetic moment
on the basis of spin only formula.
Ans. 58Ce = [Xe]54 4f 1 5d1 6s 2
Ce3+ = [Xe]54 4f 1, i.e., there is only one unpaired electron, i.e., n = 1.
Hence, µ = n (n ! 2) " 1(1 ! 2) = 3 = 1.73 BM
Q. 32. Name the members of the lanthanoid series which exhibit +4 oxidation states and those which exhibit
+2 oxidation states. Try to correlate this type of behaviour with the electronic configuration of these
elements.
Ans. + 4 = 58Ce, 59Pr, 60Nd, 65Tb, 66Dy
+ 2 = 60Nd, 62Sm, 63Eu, 69Tm, 70Yb
+2 oxidation state is exhibited when the lanthanoid has the configuration 5d 0 6s 2 so that 2 electrons are
easily lost. +4 oxidation state is exhibited when the configuration left is close to 4f 0 (e.g., 4f 0 , 4f 1, 4f 2) or
close to 4f 7 (e.g., 4f 7 or 4f 8 )
Q. 33. Compare the chemistry of the actinoids with that of landthanoids with reference to:
(i) electronic configuration (ii) oxidation states and
(iii) chemical reactivity
Ans.
S.No. Characteristics Lanthanoids Actinoids
(i) Electronic configuration [Xe] 4f 1 – 14 5d 0 – 1 6s2 [Rn] 5f 1 – 14 6d 0 – 1 7s2
(ii) Oxidation states Besides +3 O.S lanthanoids show Besides +3 O.S actinoids show higher O.S
+2 and +4 O.S only in a few cases. of +4, +5, +6, +7 also because of smaller
energy gap between 5f, 6d and 7s subshell.
(iii) General chemical These are less reactive metals. These are highly reactive metals.
reactivity of elements
Lesser tendency towards complex Greater tendency towards complex
formation. formation.
Do not form oxocation. Form oxocation.
Compounds are less basic. Compounds are more basic.
Q. 34. Write the electronic configurations of the elements with atomic numbers 61, 91, 101 and 109.
Ans. Z = 61 (Promethium, Pm), E.C. = [Xe] 4f 5 5d 0 6s2
Z = 91 (Protactium, Pa), E.C. = [Rn] 5f 2 6d 1 7s2
Z = 101 (Mendelevium, Md), E.C. = [Rn] 5f 13 6d 0 7s2
Z = 109 (Meitnerium, Mt), E.C. = [Rn] 5f 14 6d 7 7s2
Q. 35. Compare the general characteristics of the first series of transition metals with those of the second
and third series metals in the respective vertical columns on the basis of following points:
(i) electronic configurations, (ii) oxidation states,
(iii) ionisation enthalpies, and (iv) atomic sizes.
Ans. (i) Electronic configurations: The elements in the same vertical column generally have similar electronic
configurations. Although, the first series shows only two exceptions, i.e., Cr = [Ar] 3d 5 4s1 and
Cu = [Ar] 3d10 4s1 but the second series shows more exceptions, e.g., Mo(42) = [Kr] 4d5 5s1,
Ru(44) = [Kr] 4d7 5s1, Rh(45) = [Kr] 4d8 5s1, Pd(46) = [Kr] 4d10 5s 0, Ag(47) = [Kr] 4d10 5s1. Similarly,
in the third series, W(74) = [Xe] 4f 14 5d 4 6s 2, Pt(78) = [Xe] 4f 14 5d 9 6s1 and Au(79) = [Xe] 4f 14
5d10 6s1. Hence, in the same vertical column, in a number of cases, the electronic configuration of the
three series are not similar.

316 Xam idea Chemistry–XII

 (ii) Oxidation states: The elements in the same vertical column generally show similar oxidation states.
The number of oxidation states shown by the elements in the middle of each series is maximum and
minimum at the extreme ends.
(iii) Ionisation enthalpies: The first ionisation enthalpies in each series generally increase gradually as
we move from left to right though some exceptions are observed in each series. The first ionisation
enthalpies of some elements in the second (4d) series are higher while some of them have lower value
than the elements of 3d- series in the same vertical column. However, the first ionisation enthalpies
of third (5d) series are higher than those of 3d and 4d- series. This is because of weak shielding of
nucleus of 4f-electrons in the 5d-series.
(iv) Atomic sizes: Generally, ions of the same charge or atoms in a given series show progressively
decrease in radius with increasing atomic number though the decrease is quite small. But the size of
the atoms of the 4d-series is larger than the corresponding elements of the 3d-series whereas those of
corresponding elements of the 5d-series are nearly the same as those of 4d-series due to lanthanoid
contraction.
Q. 36. Write down the number of 3d electrons in each of the following ions:
Ti2+, V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+.
Indicate how would you expect the five 3d-orbitals to be occupied for these hydrated ions (octahedral).
Ans. Ions Electronic No. of 3d 3d-orbitals occupied
Configurations electrons
e g
2+ 2 2
(i ) Ti [Ar]3d 2 t 2g t 2g
eg
2+ 3 3
(ii) V [Ar]3d 3 t 2g t 2g
eg
3+ 3 3
(iii) Cr [Ar]3d 3 t 2g t 2g
eg
2+ 5 3 2
(iv) Mn [Ar]3d 5 t 2g e g t 2g
eg
2+ 6 4 2
(v ) Fe [Ar]3d 6 t 2g e g t 2g
eg
3+ 5 3 2
(vi) Fe [Ar]3d 5 t 2g e g t 2g
eg
2+ 7 5 2
(vii) Co [Ar]3d 7 t 2g e g t 2g
eg
2+ 8 6 2
(viii) Ni [Ar]3d 8 t 2g e g t 2g
eg
2+ 9 6 3
(ix) Cu [Ar]3d 9 t 2g e g t 2g
Q. 37. Comment on the statement that elements of the first transition series possess many properties
different from those of heavier transition elements. [HOTS]
Ans. The given statement is true. Some evidences in support of this statement are:
(i) Atomic radii of the heavier transition elements (4d and 5d- series) are larger than those of the
corresponding elements of the first transition series though those of 4d and 5d- series are very close
to each other.
(ii) Ionisation enthalpies of 5d- series are higher than the corresponding elements of 3d and 4d- series.
(iii) Enthalpies of atomisation of 4d and 5d- series are higher than the corresponding elements of the first series.
(iv) Melting and boiling points of heavier transition elements are greater than those of the first transition
series due to stronger intermetallic bonding.

The d- and f- Block Elements 317

Q. 38. What can be inferred from the magnetic moment values of the following complex species?
Example Magnetic Moment (BM)
K4[Mn(CN)6] 2.2
[Fe(H2O)6]2+ 5.3
K2[MnCl4] 5.9
Ans. Magnetic moment (µ) = n (n + 2) BM

For n = 1, µ = 1 (1 ! 2) " 3 " 1.73; For n = 2, µ = 2(2 + 2) " 8 " 2.83

For n = 3, µ = 3 (3 ! 2) " 15 " 3.87; For n = 4, µ = 4(4 + 2) " 24 " 4.90
For n = 5, µ = 5 (5 ! 2) " 35 " 5.92
K4[Mn(CN)6]
Here, Mn is in +2 oxidation state, i.e., as Mn2+, µ = 2.2 BM shows that it has only one unpaired electron.
Hence, when CN – ligands approach Mn2+ ion, the electrons in 3d-subshell pair up.
Hence, CN – is a strong ligand. The hybridisation involved is d 2sp3 forming inner orbital octahedral complex.
3d 4s 4p

25Mn

3d 4s 4p
2+
Mn
3d 4s 4p
[Mn(CN)6] 4– XX = Electron pair from
XX XX XX XX XX XX –
CN ions
2 3
d sp hybrid
2+
[Fe(H2O)6]
Here, Fe is in +2 oxidation state, i.e., as Fe2+. µ = 5.3 BM shows that there are four unpaired electrons. This
means that the electrons in 3d-subshell do not pair up when the ligand H2O molecules approach. Hence,
H2O is a weak ligand. To accommodate the electrons donated by six H2O molecules, the hybridisation will
be sp 3d 2. Hence, it will be an outer orbital octahedral complex.
3d 4s 4p 4d

26Fe

3d 4s 4p 4d
2+
Fe
3d 4s 4p 4d
XX = Electron pair
[Fe(H2O)6]2+ XX XX XX XX XX XX from H2O
3 2
sp d hybrid

K2[MnCl4]
Here, Mn is in +2 state, i.e., as Mn2+. µ = 5.9 BM shows that there are five unpaired electrons. Hence, the
hybridisation involved will be sp 3 and the complex will be tetrahedral.
3d 4s 4p
2+
Mn
4s 4p
2– –
[MnCl4] XX XX XX XX XX = Electron pair from Cl ions

sp3 hybrid

318 Xam idea Chemistry–XII